Abstract This paper investigates the pressure-induced photoluminescence properties and structural phase transitions of functional material NdF3 at room temperature using diamond anvil cell (DAC), in-situ photoluminescence technology, and simulation calculations. Under hydrostatic experimental pressure and simulated pressure up to 20 GPa, the photoluminescence spectra, lattice parameters, and bond lengths of NdF3 were obtained, showing their variations with pressure. Experimental results show that a new emission line, corresponding to the 4F3/2→4I9/2 transition of Nd3+ ions, appears around 12 GPa and persists up to the highest pressure of the experiment. Upon decompression, the new emission line disappears, indicating a reversible phase transition. Notably, from 0 to 12 GPa, the emission intensity of NdF3 decreases significantly under pressure, which may be attributed to the increased energy of lattice phonons in the compressed crystal (shorter Nd-F bonds), leading to enhanced phonon-assisted non-radiative relaxation.